Synthetic porous crystalline MCM-71, its synthesis and use

ABSTRACT

This invention relates to a new synthetic porous crystalline material, designated MCM-71, a method for its preparation and its use in catalytic conversion of organic compounds. The new crystalline material exhibits a distinctive X-ray diffraction pattern and has a unique 3-dimensional channel system comprising generally straight, highly elliptical channels, each of which is defined by 10-membered rings of tetrahedrally coordinated atoms, intersecting with sinusoidal channels, each of which is defined by 8-membered rings of tetrahedrally coordinated atoms.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a novel synthetic porous crystalline material,MCM-71, to a method for its preparation and to its use in catalyticconversion of organic compounds.

2. Description of the Prior Art

Zeolitic materials, both natural and synthetic, have been demonstratedin the past to have catalytic properties for various types ofhydrocarbon conversion. Certain zeolitic materials are ordered, porouscrystalline aluminosilicates having a definite crystalline structure asdetermined by X-ray diffraction, within which there are a large numberof smaller cavities which may be interconnected by a number of stillsmaller channels or pores. These cavities and pores are uniform in sizewithin a specific zeolitic material. Since the dimensions of these poresare such as to accept for adsorption molecules of certain dimensionswhile rejecting those of larger dimensions, these materials have come tobe known as “molecular sieves” and are utilized in a variety of ways totake advantage of these properties.

Such molecular sieves, both natural and synthetic, include a widevariety of positive ion-containing crystalline silicates. Thesesilicates can be described as a rigid three-dimensional framework ofSiO₄ and Periodic Table Group IIIA element oxide, e.g., AlO₄, in whichthe tetrahedra are cross-linked by the sharing of oxygen atoms wherebythe ratio of the total Group IIIA element, e.g., aluminum, and siliconatoms to oxygen atoms is 1:2. The electrovalence of the tetrahedracontaining the Group IIIA element, e.g., aluminum, is balanced by theinclusion in the crystal of a cation, for example an alkali metal or analkaline earth metal cation. This can be expressed wherein the ratio ofthe Group IIIA element, e.g., aluminum, to the number of variouscations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. One type ofcation may be exchanged either entirely or partially with another typeof cation utilizing ion exchange techniques in a conventional manner. Bymeans of such cation exchange, it has been possible to vary theproperties of a given silicate by suitable selection of the cation. Thespaces between the tetrahedra are occupied by molecules of water priorto dehydration.

Prior art techniques have resulted in the formation of a great varietyof synthetic zeolites. Many of these zeolites have come to be designatedby letter or other convenient symbols, as illustrated by zeolite A (U.S.Pat. No. 2,882,243); zeolite X (U.S. Pat. No. 2,882,244); zeolite Y(U.S. Pat. No. 3,130,007); zeolite ZK-5 (U.S. Pat. No. 3,247,195);zeolite ZK-4 (U.S. Pat. No. 3,314,752); zeolite ZSM-5 (U.S. Pat. No.3,702,886); zeolite ZSM-11 (U.S. Pat. No. 3,709,979); zeolite ZSM-12(U.S. Pat. No. 3,832,449), zeolite ZSM-20 (U.S. Pat. No. 3,972,983);ZSM-35 (U.S. Pat. No. 4,016,245); zeolite ZSM-23 (U.S. Pat. No.4,076,842); zeolite MCM-22 (U.S. Pat. No. 4,954,325); and zeolite MCM-35(U.S. Pat. No. 4,981,663), merely to name a few.

The SiO₂/Al₂O₃ ratio of a given zeolite is often variable. For example,zeolite X can be synthesized with SiO₂/Al₂O₃ ratios of from 2 to 3;zeolite Y, from 3 to about 6. In some zeolites, the upper limit of theSiO₂/Al₂O₃ ratio is unbounded. ZSM-5 is one such example wherein theSiO₂/Al₂O₃ ratio is at least 5 and up to the limits of presentanalytical measurement techniques. U.S. Pat. No. 3,941,871 (Re. U.S.Pat. No. 29,948) discloses a porous crystalline silicate made from areaction mixture containing no deliberately added alumina in thestarting mixture and exhibiting the X-ray diffraction patterncharacteristic of ZSM-5. U.S. Pat. Nos. 4,061,724; 4,073,865 and4,104,294 describe crystalline silicates of varying alumina and metalcontent.

Many zeolites are synthesized in the presence of an organic directingagent, such as an organic nitrogen compound. For example, ZSM-5 may besynthesized in the presence of tetrapropylammonium cations and zeoliteMCM-22 may be synthesized in the presence of hexamethyleneimine. It isalso possible to synthesize zeolites and related molecular sieves in thepresence of rigid polycyclic quaternary directing agents (see, forexample U.S. Pat. Nos. 5,501,848 and 5,225,179), flexible diquaternarydirecting agents (Zeolites, [1994], 14, 504) and rigid polycyclicdiquaternary directing agents (JACS, [1992], 114, 4195).

SUMMARY OF THE INVENTION

The present invention is directed to a novel porous crystallinematerial, named MCM-71, a method for its preparation, and the conversionof organic compounds contacted with an active form thereof. The calcinedform of the porous crystalline material of this invention possesses avery high acid activity and exhibits a high sorption capacity. MCM-71 isreproducibly synthesized by the present method in high purity.

DESCRIPTION OF DRAWINGS

FIG. 1 is a plan view of the elliptical 10-membered ring channels ofMCM-71.

FIG. 2 is a three dimensional view of the pore structure of MCM-71showing the tortuous 8-membered ring channels intersecting theelliptical 10-membered ring channels.

FIG. 3 shows the X-ray diffraction pattern of the as-synthesized productof Example 1.

FIG. 4 shows the X-ray diffraction pattern of the as-calcined product ofExample 1.

FIG. 5 shows the X-ray diffraction pattern of the as-synthesized productof Example 2.

FIG. 6 shows the X-ray diffraction pattern of the as-synthesized productof Example 3.

FIG. 7 shows the X-ray diffraction pattern of the as-synthesized productof Example 4.

DESCRIPTION OF SPECIFIC EMBODIMENTS

The synthetic porous crystalline material of this invention, MCM-71, isa single crystalline phase which has a unique 3-dimensional channelsystem comprising generally straight, highly elliptical channels, eachof which is defined by 10-membered rings of tetrahedrally coordinatedatoms, intersecting with sinusoidal channels, each of which is definedby 8-membered rings of tetrahedrally coordinated atoms. The 10-memberedring channels have cross-sectional dimensions of about 6.5 Angstrom byabout 4.3 Angstrom, whereas the 8-membered ring channels havecross-sectional dimensions of about 4.7 Angstrom by about 3.6 Angstrom.The pore structure of MCM-71 is illustrated in FIGS. 1 and 2 (which showonly the tetrahedral atoms), in which FIG. 1 is a plan view in thedirection view of the elliptical 10-membered ring channels and FIG. 2 isa three dimensional view showing the toruous 8-membered ring channelsintersecting the elliptical 10-membered ring channels.

The structure of MCM-71 may be defined by its unit cell, which is thesmallest structural unit containing all the structural elements of thematerial. Table 1 lists the positions of each tetrahedral atom in theunit cell in nanometers; each tetrahedral atom is bonded to an oxygenatom which is also bonded to an adjacent tetrahedral atom. Since thetetrahedral atoms may move about due to other crystal forces (presenceof inorganic or organic species, for example), a range of ±0.05 nm isimplied for each coordinate position.

TABLE 1 Number Atom x (Å) y (Å) z (Å)  1 Si1  3.721 1.856 8.420  2 Si2 3.721 1.151 11.470  3 Si3  1.540 4.009 8.190  4 Si4  1.548 2.858 12.851 5 Si5  3.721 7.424 18.010  6 Si6  3.721 8.129 1.880  7 Si7  5.901 5.27117.780  8 Si8  5.893 6.421 3.261  9 Si9  3.721 11.135 1.170 10 Si103.721 10.430 17.300 11 Si11 5.901 13.288 1.400 12 Si12 5.893 12.13815.919 13 Si13 3.721 16.703 10.760 14 Si14 3.721 17.408 7.710 15 Si151.540 14.550 10.990 16 Si16 1.548 15.701 6.329 17 Si17 5.901 14.55010.990 18 Si18 5.893 15.701 6.329 19 Si19 1.540 13.288 1.400 20 Si201.548 12.138 15.919 21 Si21 1.540 5.271 17.780 22 Si22 1.548 6.421 3.26123 Si23 5.901 4.009 8.190 24 Si24 5.893 2.858 12.851 25 Si25 0.00011.135 8.420 26 Si26 0.000 10.430 11.470 27 Si27 5.261 13.288 8.190 28Si28 5.268 12.138 12.851 29 Si29 0.000 16.703 18.010 30 Si30 0.00017.408 1.880 31 Si31 2.180 14.550 17.780 32 Si32 2.173 15.701 3.261 33Si33 0.000 1.856 1.170 34 Si34 0.000 1.151 17.300 35 Si35 2.180 4.0091.400 36 Si36 2.173 2.858 15.919 37 Si37 0.000 7.424 10.760 38 Si380.000 8.129 7.710 39 Si39 5.261 5.271 10.990 40 Si40 5.268 6.421 6.32941 Si41 2.180 5.271 10.990 42 Si42 2.173 6.421 6.329 43 Si43 5.261 4.0091.400 44 Si44 5.268 2.858 15.919 45 Si45 5.261 14.550 17.780 46 Si465.268 15.701 3.261 47 Si47 2.180 13.288 8.190 48 Si48 2.173 12.13812.851

MCM-71 can be prepared in essentially pure form with little or nodetectable impurity crystal phases. In its calcined form, MCM-71 has anX-ray diffraction pattern which, although resembling that of DCM-2(disclosed in U.S. Pat. No. 5,397,550), is distinguished therefrom andfrom the patterns of other known as-synthesized or thermally treatedcrystalline materials by the lines listed in Table 2 below.

TABLE 2 Relative d_(hkl) Å. Intensity 9.57 ± 0.100 w-s 9.28 ± 0.070 w-s8.35 ± 0.050 m-s 6.50 ± 0.040 w-m 5.26 ± 0.030 w-m 4.79 ± 0.030 m-s 4.18± 0.020 vw-w 3.75 ± 0.020 w-m 3.54 ± 0.020 s-vs 3.45 ± 0.014 s-vs 3.35 ±0.010 w 3.14 ± 0.010 vw-w 2.95 ± 0.008 vw-w 1.86 ± 0.025 vw

These X-ray diffraction data were collected with a Scintag diffractionsystem, equipped with a germanium solid-state detector, using copperK-alpha radiation. The diffraction data were recorded by step-scanningat 0.02 degrees of two-theta, where theta is the Bragg angle, and acounting time of 10 seconds for each step. The interplanar spacings,d's, were calculated in Angstrom units, and the relative intensities ofthe lines, I/I₀ (where I₀ is one-hundredth of the intensity of thestrongest line, above background), were derived with the use of aprofile fitting routine (or second derivative algorithm). Theintensities are uncorrected for Lorentz and polarization effects. Therelative intensities are given in terms of the symbols vs=very strong(80-100), s=strong (60-80), m=medium (40-60), w=weak (20-40), andvw=very weak (0-20). It should be understood that diffraction datalisted for this sample as single lines may consist of multipleoverlapping lines which under certain conditions, such as differences incrystallographic changes, may appear as resolved or partially resolvedlines. Typically, crystallographic changes can include minor changes inunit cell parameters and/or a change in crystal symmetry, without achange in the structure. These minor effects, including changes inrelative intensities, can also occur as a result of differences incation content, framework composition, nature and degree of porefilling, crystal size and shape, preferred orientation and thermaland/or hydrothermal history.

The crystalline material of this invention has a composition involvingthe molar relationship:

X₂O₃:(n)YO₂,

wherein X is a trivalent element, such as aluminum, boron, iron, indium,and/or gallium, preferably aluminum; Y is a tetravalent element such assilicon, tin, titanium and/or germanium, preferably silicon; and n is atleast about 2, such as 4 to 1000, and usually from about 5 to about 100.In the as-synthesized form, the material has a formula, on an anhydrousbasis and in terms of moles of oxides per n moles of YO₂, as follows:

(0.1 -2)M₂O:(0-2)Q:X₂O₃:(n)YO₂

wherein M is an alkali or alkaline earth metal, normally potassium, andQ is an organic moiety, normally triethanolamine. The M and Q componentsare associated with the material as a result of their presence duringcrystallization and it will be seen from the formula of theas-synthesized species that MCM-71 can be synthesized without an organicdirecting agent. The M and Q components are easily removed bypost-crystallization methods hereinafter more particularly described.

The crystalline material of the invention is thermally stable and in thecalcined form exhibits a high surface area (380 m²/g with microporevolume of 0.14 cc/g) and significant sorption capacity for water andhydrocarbons:

14.7 wt. % for water

8.4 wt. % for normal-hexane

5.4 wt. % for cyclohexane.

To the extent desired, the original sodium and/or potassium cations ofthe as-synthesized material can be replaced in accordance withtechniques well known in the art, at least in part, by ion exchange withother cations. Preferred replacing cations include metal ions, hydrogenions, hydrogen precursor, e.g., ammonium ions and mixtures thereof.Particularly preferred cations are those which tailor the catalyticactivity for certain hydrocarbon conversion reactions. These includehydrogen, rare earth metals and metals of Groups IIA, IIIA, IVA, VA, IB,IIB, IIIB, IVB, VB, VIB, VIIB and VIII of the Periodic Table of theElements.

When used as a catalyst, the crystalline material of the invention maybe subjected to treatment to remove part or all of any organicconstituent. This is conveniently effected by thermal treatment in whichthe as-synthesized material is heated at a temperature of at least about370° C. for at least 1 minute and generally not longer than 20 hours.While subatmospheric pressure can be employed for the thermal treatment,atmospheric pressure is desired for reasons of convenience. The thermaltreatment can be performed at a temperature up to about 925° C. Thethermally treated product, especially in its metal, hydrogen andammonium forms, is particularly useful in the catalysis of certainorganic, e.g., hydrocarbon, conversion reactions.

When used as a catalyst, the crystalline material can be intimatelycombined with a hydrogenating component such as tungsten, vanadium,molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noblemetal such as platinum or palladium where ahydrogenation-dehydrogenation function is to be performed. Suchcomponent can be in the composition by way of cocrystallization,exchanged into the composition to the extent a Group IIIA element, e.g.,aluminum, is in the structure, impregnated therein or intimatelyphysically admixed therewith. Such component can be impregnated in or onto it such as, for example, by, in the case of platinum, treating thesilicate with a solution containing a platinum metal-containing ion.Thus, suitable platinum compounds for this purpose includechloroplatinic acid, platinous chloride and various compounds containingthe platinum amine complex.

The crystalline material of this invention, when employed either as anadsorbent or as a catalyst in an organic compound conversion processshould be dehydrated, at least partially. This can be done by heating toa temperature in the range of 200° C. to about 370° C. in an atmospheresuch as air, nitrogen, etc. and at atmospheric, subatmospheric orsuperatmospheric pressures for between 30 minutes and 48 hours.Dehydration can also be performed at room temperature merely by placingthe MCM-71 in a vacuum, but a longer time is required to obtain asufficient amount of dehydration.

The present crystalline material can be prepared from a reaction mixturecontaining sources of alkali or alkaline earth metal (M) cation,normally potassium, an oxide of trivalent element X, e.g., aluminumand/or boron, an oxide of tetravalent element Y, e.g., silicon, andwater, said reaction mixture having a composition, in terms of moleratios of oxides, within the following ranges:

Reactants Useful Preferred YO₂/X₂O₃     2-100,000  5-100 H₂O/YO₂ 10-1000 20-50 OH⁻/YO₂ 0.02-2   0.1-0.8 M/YO₂ 0.02-2   0.1-0.8

MCM-71 can be crystallized from a completely inorganic synthesis mixtureor alternatively can be produced in the presence of an directing agent(Q), preferably triethanolamine. Where a directing agent is present, themolar ratio Q/YO₂ is typically 0.01-2.0 and preferably is 0.1-0.3.

Crystallization of MCM-71 can be carried out at either static or stirredconditions in a suitable reactor vessel, such as for example,polypropylene jars or teflon lined or stainless steel autoclaves, at atemperature of 100° C. to about 220° C. for a time sufficient forcrystallization to occur at the temperature used, e.g., from about 5hours to 30 days. Thereafter, the crystals are separated from the liquidand recovered.

It should be realized that the reaction mixture components can besupplied by more than one source. The reaction mixture can be preparedeither batchwise or continuously. Crystal size and crystallization timeof the new crystalline material will vary with the nature of thereaction mixture employed and the crystallization conditions.

Synthesis of the new crystals may be facilitated by the presence of atleast 0.01 percent, preferably 0.10 percent and still more preferably 1percent, seed crystals (based on total weight) of crystalline product.

The crystals prepared by the instant invention can be shaped into a widevariety of particle sizes. Generally speaking, the particles can be inthe form of a powder, a granule, or a molded product, such as anextrudate having particle size sufficient to pass through a 2 mesh(Tyler) screen and be retained on a 400 mesh (Tyler) screen. In caseswhere the catalyst is molded, such as by extrusion, the crystals can beextruded before drying or partially dried and then extruded.

The crystalline material of this invention can be used to catalyze awide variety of chemical conversion processes, particularly organiccompound conversion processes, including many of presentcommercial/industrial importance. Examples of chemical conversionprocesses which are effectively catalyzed by the crystalline material ofthis invention, by itself or in combination with one or more othercatalytically active substances including other crystalline catalysts,include those requiring a catalyst with acid activity.

Thus, in its active, hydrogen form MCM-71 exhibits a high acid activity,with an alpha value of 20 to 45. Alpha value is an approximateindication of the catalytic cracking activity of the catalyst comparedto a standard catalyst and it gives the relative rate constant (rate ofnormal hexane conversion per volume of catalyst per unit time). It isbased on the activity of silica-alumina cracking catalyst taken as anAlpha of 1 (Rate Constant=0.016 sec-1). The Alpha Test is described inU.S. Pat. No. 3,354,078; in the Journal of Catalysis, 4, 527 (1965); 6,278 (1966); and 61, 395 (1980), each incorporated herein by reference asto that description. The experimental conditions of the test used hereininclude a constant temperature of 538° C. and a variable flow rate asdescribed in detail in the Journal of Catalysis, 61, 395 (1980).

As in the case of many catalysts, it may be desirable to incorporate thenew crystal with another material resistant to the temperatures andother conditions employed in organic conversion processes. Suchmaterials include active and inactive materials and synthetic ornaturally occurring zeolites as well as inorganic materials such asclays, silica and/or metal oxides such as alumina. The latter may beeither naturally occurring or in the form of gelatinous precipitates orgels including mixtures of silica and metal oxides. Use of a material inconjunction with the new crystal, i.e., combined therewith or presentduring synthesis of the new crystal, which is active, tends to changethe conversion and/or selectivity of the catalyst in certain organicconversion processes. Inactive materials suitably serve as diluents tocontrol the amount of conversion in a given process so that products canbe obtained economically and orderly without employing other means forcontrolling the rate of reaction. These materials may be incorporatedinto naturally occurring clays, e.g., bentonite and kaolin, to improvethe crush strength of the catalyst under commercial operatingconditions. Said materials, i.e., clays, oxides, etc., function asbinders for the catalyst. It is desirable to provide a catalyst havinggood crush strength because in commercial use it is desirable to preventthe catalyst from breaking down into powder-like materials. These clayand/or oxide binders have been employed normally only for the purpose ofimproving the crush strength of the catalyst.

Naturally occurring clays which can be composited with the new crystalinclude the montmorillonite and kaolin family, which families includethe subbentonites, and the kaolins commonly known as Dixie, McNamee,Georgia and Florida clays or others in which the main mineralconstituent is halloysite, kaolinite, dickite, nacrite, or anauxite.Such clays can be used in the raw state as originally mined or initiallysubjected to calcination, acid treatment or chemical modification.Binders useful for compositing with the present crystal also includeinorganic oxides, such as silica, zirconia, titania, magnesia, beryllia,alumina, and mixtures thereof.

In addition to the foregoing materials, the new crystal can becomposited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesiaand silica-magnesia-zirconia.

The relative proportions of finely divided crystalline material andinorganic oxide matrix vary widely, with the crystal content rangingfrom about 1 to about 90 percent by weight and more usually,particularly when the composite is prepared in the form of beads, in therange of about 2 to about 80 weight percent of the composite.

In order to more fully illustrate the nature of the invention and themanner of practicing same, the following examples are presented.

EXAMPLE 1 Synthesis of Aluminosilicate MCM-71

7 g of Colloidal Silica (30 wt %), Al(OH)₃ (Aluminum Hydroxide, solid),KOH (Potassium Hydroxide, 20 wt % solution), triethanolamine anddistilled water were combined in the following molar ratio:

Si/Al₂ 20 H₂O/Si 30 OH/Si 0.375 K⁺/Si 0.375 Triethanolamine/Si 0.20

The combined mixture was added to an autoclave and heated to 160° C. for368 hours and subsequently heated to 180° C. for 82 hours. The productwas then filtered and washed with water and dried overnight under an IRlamp. The solid was then calcined in air at a temperature of 540° C. for8 hours to yield the new material designated as MCM-71. The powderpatterns of the as-synthesized and calcined materials are given in FIGS.3 and 4 respectively, and show mordenite as an impurity phase (less than5%). The as-synthesized material has the corresponding peak list ascompiled in Table 3.

TABLE 3 d_(hkl) Å 100 I_(o)/I_(max) 13.58* 4.1 10.25* 2.0 9.60 25.8 9.3042.8 9.06* 10.4 8.37 58.6 6.67 4.2 6.50 41.6 6.38* >1.0 6.05* 1.7 5.80*3.5 5.27 30.5 4.80 56.5 4.70 4.6 4.65 7.8 4.52 7.5 4.34* 6.0 4.18 15.64.08* 9.8 4.05* 4.6 4.00 8.0 3.94 4.4 3.82 3.8 3.76 41.9 3.72 9.19 3.5569.29 3.46 100.0 3.40 20.0 3.35 14.2 3.28 30.3 3.25 19.8 3.22* 7.8 3.209.7 3.14 18.5 3.06 10.2 2.953 17.9 2.887* 2.9 2.872 4.8 2.804 10.8 2.78110.0 2.645 8.6 2.628 5.0 2.568 2.8 2.545 1.1 2.512 2.9 2.496 3.3 2.4823.0 2.433 1.6 2.421 2.0 2.361 1.7 2.324 1.5 2.217 >1.0 2.188 >1.02.146 >1.0 2.133 2.7 2.077* 2.7 2.049 >1.0 2.023 2.8 1.987 1.5 1.972 2.71.961 2.4 1.950 2.4 1.935 2.1 1.917 >1.0 1.878 1.7 1.861 7.5 1.824 2.0*denotes a probable impurity peak

EXAMPLE 2 Synthesis of Aluminosilicate MCM-71

7 g of Colloidal Silica (30 wt %), Al(OH)₃ (Aluminum Hydroxide, solid),KOH (Potassium Hydroxide, 20 wt % solution), triethanolamine anddistilled water were combined in the following ratio:

Si/Al₂ 21 H₂O/Si 30 OH/Si 0.375 K⁺/Si 0.375 Triethanolamine/Si 0.20

The combined mixture was added to an autoclave and heated to 160° C. for360 hours and subsequently heated to 180° C. for 120 hours. The productwas then filtered and washed with water and dried overnight under an IRlamp. The powder pattern of the as-synthesized material is given in FIG.5.

EXAMPLE 3 Synthesis of Aluminosilicate MCM-71

7 g of Colloidal Silica (30 wt %), Al(OH)₃ (Aluminum Hydroxide, solid),KOH (Potassium Hydroxide, 20 wt % solution) and distilled water werecombined in the following ratio:

Si/Al₂ 20 H₂O/Si 30 OH/Si 0.375 K⁺/Si 0.375

The combined mixture was added to an autoclave and heated to 160° C. for300 hours and subsequently heated to 180° C. for 132 hours. The productwas then filtered and washed with water and dried overnight under an IRlamp. The powder pattern of the as-synthesized material is given in FIG.6.

EXAMPLE 4 Synthesis of Aluminosilicate MCM-71

7 g of Colloidal Silica (30 wt %), Al(OH)₃ (Aluminum Hydroxide, solid),KOH (Potassium Hydroxide, 20 wt % solution) and distilled water werecombined in the following ratio:

Si/Al₂ 22 H₂O/Si 30 OH/Si 0.375 K⁺/Si 0.375

The combined mixture was added to an autoclave and heated to 160° C. for300 hours and subsequently heated to 180° C. for 132 hours. The productwas then filtered and washed with water and dried overnight under an IRlamp. The powder pattern of the as-synthesized material is given in FIG.7 and the corresponding peak list is compiled in Table 4.

TABLE 4 d Å 100 I/I 13.45* 1.8 10.17* 1.2 9.51 24.1 9.24 35.3 8.99* 5.98.32 51.0 6.63 6.3 6.47 39.3 6.02* 1.0 5.77* 1.5 5.24 29.6 4.96* 0.324.77 59.5 4.67 6.2 4.63 7.6 4.50 4.4 4.31* 6.1 4.25 13.6 4.17 15.7 4.07*18.5 4.03* 11.6 3.98* 5.4 3.93 5.1 3.81 3.6 3.75 43.2 3.71 9.23.63* >1.0 3.53 74.8 3.446 100.0 3.39 20.9 3.34 74.9 3.27 32.7 3.22 19.93.19 6.8 3.13 30.0 3.05 11.2 3.03 4.6 2.945 20.5 2.865 4.2 2.796 11.92.774 9.4 2.639 8.7 2.620 6.3 2.561 2.8 2.483 3.6 2.455* 3.8 2.417 1.32.355 2.4 2.317 1.6 2.281 3.3 2.239 2.0 2.213 1.3 2.183 >1.0 2.128 5.02.072 3.3 2.018 3.3 1.981 2.2 1.969 2.2 1.959 1.2 1.944 1.9 1.930 1.71.876 1.4 *denotes a probable impurity peak.

What is claimed is:
 1. A synthetic porous crystalline material with aframework of tetrahedral atoms bridged by oxygen atoms, the tetrahedralatom framework being defined by a unit cell with atomic coordinates innanometers shown in Table 1, wherein each coordinate position may varywithin ±0.05 nm.
 2. A synthetic porous crystalline materialcharacterized by an X-ray diffraction pattern including valuessubstantially as set forth in Table 2 of the specification.
 3. Thecrystalline material of claim 2 having a composition comprising themolar relationship X₂O₃:(n)YO₂, wherein n is at least about 2, X is atrivalent element, and Y is a tetravalent element.
 4. The crystallinematerial of claim 3 having a composition, on an anhydrous basis and interms of moles of oxides per n moles of YO₂, expressed by the formula:(0.1-2)M₂O:(0-2)Q:X₂O₃:(n)YO₂ wherein M is alkali or alkaline earthmetal and Q is an organic moiety.
 5. The crystalline material of claim 4wherein said Q comprises a cation derived from triethanolamine.
 6. Thecrystalline material of claim 3 wherein X is a trivalent elementselected from the group consisting of boron, iron, indium, gallium,aluminum, and a combination thereof; and Y is a tetravalent elementselected from the group consisting of silicon, tin, titanium, germanium,and a combination thereof.
 7. The crystalline material of claim 3wherein X comprises aluminum and Y comprises silicon.
 8. The crystallinematerial of claim 3 wherein n is about 5 to about
 100. 9. A method forsynthesizing crystalline material exhibiting a characteristic X-raydiffraction pattern including d-spacing maxima values shown in Table 2which comprises (i) preparing a mixture capable of forming saidmaterial, said mixture comprising sources of alkali or alkaline earthmetal (M), an oxide of trivalent element (X), an oxide of tetravalentelement (Y) and water, having a composition, in terms of mole ratios,within the following ranges: YO₂/X₂O₃     2-100,000 H₂O/YO₂  10-1000OH⁻/YO₂ 0.02-2   M/YO₂ 0.02-2  

(ii) maintaining said mixture under sufficient conditions including atemperature of from about 100° C. to about 220° C. until crystals ofsaid material are formed; and (iii) recovering said crystalline materialfrom step (ii).
 10. The method of claim 9 wherein said mixture has acomposition, in terms of mole ratios, within the following ranges:YO₂/X₂O₃  5-100 H₂O/YO₂ 20-50 OH⁻/YO₂ 0.1-0.8 M/YO₂  0.1-0.8.


11. The method of claim 9 wherein M is potassium.
 12. The method ofclaim 9 wherein said mixture contains a directing agent (Q) comprisingtriethanolamine in an amount such that the molar ratio of Q/YO₂ is about0.01 to about 2.0.
 13. A process for converting a feedstock comprisingorganic compounds to conversion product which comprises contacting saidfeedstock at organic compound conversion conditions with a catalystcomprising an active form of the synthetic porous crystalline materialof claim 1.